CN102978494B - Mg-Ge magnesium alloy and preparation method thereof - Google Patents
Mg-Ge magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Mg-Ge magnesium alloy and a preparation method thereof. The magnesium alloy comprises Mg and Ge; and the content of Ge in the magnesium alloy is 0-5 wt%, but is not zero. The preparation method of the magnesium alloy comprises the following steps: mixing the Mg, Ge, Ca, Zn and microelements in any of the following modes 1)-6) to obtain a mixture: 1) Mg and Ge; 2) Mg, Ge and Ca; 3) Mg, Ge and Zn; 4) Mg, Ge and microelements; 5) Mg, Ge, Ca and microelements; and 6) Mg, Ge, Zn and microelements; and carrying out vacuum smelting on the mixture or sintering the mixture, and cooling to obtain the magnesium alloy. In order to improve the characteristics of low mechanical properties and poor corrosion resistance in the traditional medical magnesium alloy, the biodegradable and bioabsorbable Mg-Ge-(Ca, Zn) alloy disclosed by the invention adopts Ge, Ca and Zn with favorable biocompatibility as alloying elements, and combines the composition design and preparation technique, thereby implementing the regulation and control on the mechanical properties and corrosion resistance of the magnesium alloy.
Description
Technical field
The present invention relates to a kind of Mg-Ge magnesium alloy and preparation method thereof, belong to Medical magnesium alloy material and preparation method thereof field.
Background technology
At present, the biomedical metallic material of widespread use clinically mainly comprises 316L, 317L, 304V stainless steel, Co-Cr-Mo alloy, pure titanium, Ti-6Al-4V, TiNi alloy etc.The implant that these materials are prepared from possesses the biocompatibility of good mechanical property, corrosion resistance nature and excellence, is usually used to damaged tissue or auxiliary trauma repair in alternative body clinically.When it is used to damaged tissue in alternative body, require that implant can long-term holding structure is stable in vivo state.And in most of the cases, the demand of people to implant and support provided function is in vivo all temporary transient.Because these materials are all inert materials, can not degrade voluntarily in vivo, therefore need second operation to take out, add medical expense and patient risk.In addition, implant is retained for a long time in body and can be brought not expected negative impact, and such as, the intravascular stent of inserting for a long time in body can cause inflammation and vascellum endometrial hyperplasia, and then cause vascular restenosis.
Meanwhile, its Young's modulus of these biomedical metallic materials of current widespread use and osseous tissue extremely do not match, thus cause " stress shielding " effect.Such consequence weakens the stimulation of freshman bone tissue's generation and plasticity, and the stability of implant is declined.
Magnesium is a kind of special light metal, and its density is 1.74g/cm
3, with people's bone density (1.8-2.1g/cm
3) close.Compared with other metal implant materials, its Young's modulus and compression yield strength are closer to normal bone tissues.Magnesium is the second important positively charged ion in human body, and content is only second to potassium.Magnesium normal contents in human body is 25 grams, and half is present in bone.In addition, magnesium is indispensable in human normal metabolic processes.Magnesium ion between 0.7-1.05mmol/L, keeps its concentration stabilize by kidney and small intestine at the fluctuation of concentration of extracellular fluid.The main drawback of magnesium in engineer applied is low erosion resistance, but this shortcoming has become it as the advantage of biomaterial application: magnesium can be degraded into solvable nontoxic oxide compound in vivo and harmless excreting from intestinal tissue is external.Therefore, as novel biological medical degradable material, Mg-based hydrogen storage possesses good mechanical property, corrodible degradation property and biocompatibility, has a good application prospect.
Trace element germanium plays an important role in human life's process, closely related with HUMAN HEALTH.Germanium is distributed widely in each histoorgan of human body, many enzymes in body, if guanidine propylhomoserin enzyme, cellular oxidation enzyme, carbonic anhydride enzyme and pallium, grey matter composition are all containing germanium, also contain germanium in the subcellular components such as cell walls, plastosome, lysosome and intercellular substance matrix.Grownup on average takes in germanium 0.4-3.7mg from drinking-water, food etc. every day, almost all by gastrointestinal absorption, enters blood circulation.Do not have selectivity to each tissue after germanium enters human body, usually without cumulative effect, major part is discharged in 4-7d via kidney from urine, also has part germanium directly to excrete from digestive tube with the form of ight soil.Experimental results demonstrate, germanium has the multi-functional such as antitumor, anti-inflammatory and immunomodulatory, antiviral, anti-oxidant, anti-ageing, reducing blood-fat, is a kind of trace element with good health protection effect.From materialogy angle, germanium in magnesium matrix with mesophase spherule Mg
2the form of Ge exists.The interpolation of element Ge can effective crystal grain thinning, improves mechanical property and the corrosion resistance nature of magnesium alloy.
Calcium is a kind of essential element, and be also the magnanimity metallic element that in human body, content is the abundantest, content is only second to C, H, O, N.In normal situation, in adult body, calcium contents is about 1200g, and wherein about 99% is present in bone and tooth, mainly exists with the form of hydroxyapatite crystal, and maintenance bone and tooth have hard structure and support.The calcium of about 1% is often present in the outer liquid of soft tissue cells and blood with ionic condition that is free or that combine in addition, is referred to as miscible calcium pool.Calcium plays an important role in the various physiology and chemistry process of body.From materialogy angle, calcium can remarkable crystal grain thinning, thus improves plasticity and the intensity of magnesium alloy, also can reduce the microbattery effect of magnesium alloy, improve the corrosion resistance of magnesium alloy.
Zinc is the essential trace element of human body.Zinc in body is all almost the Zn being attached to cell protein
2+form exists, it is to the high-affinity of electronics, it is very easily reacted with amino acid side chain, and formed crosslinked in polypeptide or between polypeptide, change tertiary protein structure and function, zinc plays keying action in Growth of Cells and atomization, and what therefore ZD detrimentally affect was outstanding shows immunity system.On metallurgy, the maximum solid solution degree of zinc in magnesium is 6.2%, is a kind of effective alloy element in addition to aluminum, has the effect of solution strengthening and ageing strengthening.Magnesium alloy room temperature strength can be significantly improved, improve the erosion resistance of magnesium alloy.
Summary of the invention
The object of this invention is to provide a kind of Mg-Ge magnesium alloy and preparation method thereof, Mg-Ge magnesium alloy provided by the invention has good biocompatibility and corrosion resistance nature, and can meet the requirement of mechanical property, can be used as medical embedded material.
A kind of Mg-Ge magnesium alloy provided by the present invention, described magnesium alloy comprises Mg and Ge;
By weight percentage, in described magnesium alloy, the content of Ge can be 0 ~ 5%, but non-vanishing, and magnesium alloy provided by the invention can be dense structure or vesicular structure.
In above-mentioned magnesium alloy, described magnesium alloy also comprises Ca, and the mass percentage of described Ca can be 0 ~ 2%, but non-vanishing.
In above-mentioned magnesium alloy, described magnesium alloy also comprises Zn, and the mass percentage of described Zn can be 0 ~ 2%, but non-vanishing.
In above-mentioned magnesium alloy, described magnesium alloy also comprises trace element, and described trace element is at least one in manganese, zirconium, tin, rare earth and yttrium;
In described magnesium alloy, the mass percentage of described trace element can be 0 ~ 2%, but non-vanishing and 2%.
In above-mentioned magnesium alloy, in described magnesium alloy, the mass percentage of manganese is not more than 1.5%, the mass percentage of zirconium is not more than 1%, the mass percentage of tin is not more than 2%, and the mass percentage of rare earth is not more than 2%, and the mass percentage of yttrium is not more than 1%.
The concrete composition of above-mentioned magnesium alloy can be: be made up of Ge and magnesium, and the mass percentage of Ge is 1.5% ~ 3%, and surplus is magnesium, specifically can be 1.5% Ge and the magnesium of surplus, the Ge of 2.5% and the magnesium of surplus or the Ge of 3% and surplus magnesium; Be made up of Ge, magnesium and Ca, the magnesium of the mass percentage of Ge to be the mass percentage of 1.5%, Ca be 0.2% ~ 1.5% and surplus, specifically can be the magnesium of the Ca of 0.2%, the Ge of 1.5% and surplus, the magnesium of the Ca of 1.5%, the Ge of 1.5% and surplus; Be made up of Ge, magnesium and Zn, the magnesium of the mass percentage of Ge to be the mass percentage of 2.5%, Zn be 1.5% and surplus.
The invention provides the preparation method of above-mentioned magnesium alloy, comprise the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any one mode carry out being mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
At CO
2and SF
6under atmosphere protection, described mixture being carried out melting, namely obtain described magnesium alloy after cooling, is dense structure.
In above-mentioned preparation method, the temperature of described melting can be 650 ~ 800 DEG C, and described smelting time can be 2 ~ 8h, as melting 5 hours under the condition of 800 DEG C.
In above-mentioned preparation method, described method also comprises the step of described magnesium alloy being carried out mechanical workout; Described mechanical workout comprises rolling and/or rapid solidification step;
Described rolling comprises the steps: described magnesium alloy to carry out solution treatment, as solution treatment 2 ~ 20 hours at 300 ~ 500 DEG C, then successively through roughing, in roll and finish rolling, as carried out roughing at 400 ~ 500 DEG C, reduction in pass is 10 ~ 15%; In to roll temperature be 350 ~ 400 DEG C, reduction in pass 30 ~ 60%; Final rolling temperature 200 ~ 350 DEG C, reduction in pass 5 ~ 10%;
Described rapid solidification comprises the steps: to adopt high vacuum fast quenching system to make rapid coagulation band under Ar gas shielded, wherein feeding quantity is 2 ~ 8g, induction heating power is 3 ~ 7kW, nozzle and roller spacing are 0.8mm, spraying pressure is 0.05 ~ 0.2MPa, roller speed is 500 ~ 5000r/min, nozzle slot size 1film × 8mm × 6mm; Then be broken into by strip Powdered, 200 ~ 350 DEG C of vacuum hotpressing 1 ~ 24h, make Mg-Ge-Zn system alloy extrusion base, then extrude within the scope of 200 ~ 400 DEG C, extrusion ratio is 10 ~ 60.
Present invention also offers the preparation method of another kind of above-mentioned magnesium alloy, comprise the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any one mode carry out being mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
Sintered by described mixture, then namely obtain described magnesium alloy through cooling, this magnesium alloy is vesicular structure;
Describedly be sintered to any one method following: element powders mixed-sintering method, prealloy powder sintering process and self-propagating high-temperature synthesis.
Described element powders mixed-sintering method comprises the steps: to sinter in Ar gas shielded atmosphere; with behind ramp to 200 ~ 500 of 2 ~ 4 DEG C/min DEG C; then with ramp to 650 ~ 800 DEG C of 30 DEG C/min; carry out sintering 1 ~ 12 hour; then the cold cooling of stove, obtains the magnesium alloy of vesicular structure, after being warming up at a slow speed 300 DEG C with 2 DEG C/min; then be rapidly heated to 700 DEG C with 30 DEG C/min, then keep 4h at this temperature.
Described prealloy powder sintering process heat-treats 10 ~ 12 hours under comprising the steps: that described mixture is placed in the condition of 300 ~ 600 DEG C, obtains the magnesium alloy of vesicular structure.
Described self-propagating high-temperature synthesis comprises the steps: under protection of inert gas, gaseous tension 1 × 10
3-1 × 10
5pa, lights described mixture and carries out SHS process, obtain the magnesium alloy of vesicular structure at 200 ~ 700 DEG C.
In above-mentioned method, absorb Mg-Ge-(Ca, Zn to improve degradable prepared by the inventive method) corrosion resistance nature of serial medical magnesium alloy, described method also comprises the step of the surface-coated degradable ceramic coating to described magnesium alloy;
The material of described degradable ceramic coating is one or more the arbitrary combination in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.
In above-mentioned preparation method, the thickness of described degradable ceramic coating can be 0.01 ~ 5mm;
Described degradable ceramic coating is applied by plasma spraying, galvanic deposit or differential arc oxidation method;
The main gas of described plasma spraying degradable ceramic coating plasma gas used: Ar 30-100scfh, secondary gas: H
25-20scfh, spraying current: 400 ~ 800A, spray voltage: 40 ~ 80V, spray distance 100 ~ 500mm.
Described galvanic deposit degradable ceramic coating is with described magnesium alloy for negative electrode, and in the electrolytic solution of material preparing degradable ceramic coating, current density is 0.5 ~ 30mA/cm
2, temperature is 25 ~ 85 DEG C, after process 10 ~ 60min, and cleaning-drying.
The method of described differential arc oxidation is by described magnesium alloy in the electrolytic solution of material preparing degradable ceramic coating, under 200 ~ 500V condition, be oxidized 5 ~ 30min.
The present invention has following beneficial effect:
Degradable provided by the invention absorbs Mg-Ge-(Ca, Zn) series alloy, in order to improve the feature that mechanical property is lower, corrosion resistance nature is poor that conventional medical magnesium alloy generally has, the germanium selecting biocompatibility good, calcium, zinc are as alloy element, by the combination of Composition Design and preparation technology, achieve the regulation and control of mechanical property to magnesium alloy and corrosion resistance nature.
Accompanying drawing explanation
Fig. 1 is Mg-Ge-(Ca, Zn prepared by embodiment 1 and embodiment 2) the metallographic microstructure figure of alloy material.
Fig. 2 is Mg-Ge-(Ca, Zn prepared by embodiment 1 and embodiment 2) the room temperature tensile properties curve of alloy.
Fig. 3 is Mg-Ge-(Ca, Zn prepared by embodiment 1 and embodiment 2) alloy carries out the corrosive nature curve that electrochemical test obtains in human simulation body fluid.
Fig. 4 is Mg-Ge-(Ca, Zn of preparing in embodiment 1 and embodiment 2) cultivate the cell survival rate of MG63 and MC-3T3 after 1,3 and 5 day in alloy material vat liquor, wherein Fig. 4 (a) and Fig. 4 (b) is respectively the cell survival rate of MG63 and MC-3T3.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, preparation as cast condition Mg-Ge-(Ca, Zn) alloy
Test raw material adopts pure Mg(99.9wt.%), Ge powder (99.9wt.%), Ca powder (99.8wt.%) and Zn powder (99.8wt.%).
Mixture is coordinated with proportioning respectively according to following component:
The Mg of (a) Ge 1.5% and surplus; The Mg of (b) Ge 2.5% and surplus; The Mg of (c) Ge 3% and surplus; The Mg of (d) Ge 1.5%, Ca 0.2% and surplus; E the Mg of () Ge 1.5%, Zn 1.5% and surplus, above-mentioned surplus refers to and is supplemented to quality to 100%.
Then the component of said ratio is placed in mortar and carries out hand mix, then in batch mixing instrument with the rotating speed mixing 5min of 2000rpm.Then mixed powder is placed in plumbago crucible, at CO
2and SF
6melting 5h is carried out under atmosphere protection condition; temperature is 700 DEG C; then melt is poured in the mould being preheating to 200 DEG C in advance; obtain as-cast magnesium alloy: Mg-1.5Ge; Mg-2.5Ge, Mg-3Ge, Mg-1.5Ge-0.2Ca and Mg-1.5Ge-1.5Ca; its micro-organization chart as shown in Figure 1, is followed successively by Fig. 1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d) and Fig. 1 (e).
Can be learnt by Fig. 1, the grain-size of magnesium alloy reduces gradually with the increase of Ge constituent content, and after adding Ca element, the grain-size of alloy increases to some extent, and the interpolation of Zn element significantly reduces the grain-size of material.
Embodiment 2, preparation roll state Mg-Ge-(Ca, Zn) alloy
First the Mg-Ge alloy cast ingot of as cast condition is prepared according to the step in embodiment 1; Mg-Ge alloy cast ingot is processed into 5mm heavy-gauge sheeting, sand papering is to no significant defect, at 400 DEG C, solution treatment 3 hours, is rolled, carry out successively roughing, in roll and finish rolling: at 450 DEG C, carry out roughing, reduction in pass is 10%, roll in carrying out at 400 DEG C, reduction in pass is 50%, at 350 DEG C, carry out roughing, reduction in pass is 10%, is finally rolled down to 2mm thin thick plate.
The present embodiment obtains rolling state magnesium alloy: Mg-1.5Ge, Mg-2.5Ge, Mg-3Ge, and as shown in Figure 1, be followed successively by Fig. 1 (f), Fig. 1 (g) and Fig. 1 (h), can be learnt by this figure, after rolling, each alloy grain size all decreases its microstructure.
Embodiment 3, Mg-Ge-(Ca, Zn) room temperature tensile properties of alloy
Mg-Ge-(Ca, Zn by prepared by embodiment 1 and embodiment 2) alloy according to ASTM-E8-04 Elongation test standard system for drawn samples, SiC sand papering is to 2000#, adopt general purpose material tensile testing machine at room temperature to carry out tension test, draw speed is 1mm/min.
Mg-Ge-(Ca, Zn prepared by the present invention) alloy room temperature tensile properties as shown in Figure 2, can be learnt by Fig. 2, with the increase of Ge content, tensile strength and the unit elongation of material all increase.The interpolation of Zn element improves intensity and the unit elongation of material simultaneously, and with the addition of the alloy strength of Ca element and unit elongation declines all to some extent.Relative to cast alloy, yield strength and the tensile strength of rolling state alloy are all significantly improved, and unit elongation then declines to some extent.
Embodiment 4, Mg-Ge-(Ca, Zn) corrosion resistance of alloy
Mg-Ge-(Ca, Zn by prepared by embodiment 1 and embodiment 2) alloy wire is cut into 10 × 10 × 2mm
3block sample, be polished to 2000# with sand papering.Then in Hank ' the s simulated body fluid of 37 DEG C, electrochemical test is carried out.
Mg-Ge-(Ca, Zn prepared by the present invention) alloy corrosion potential-corrosion current curve as shown in Figure 3, can be learnt by this figure, after rolling, the corrosion resistance nature of alloy significantly improves, show as corrosion potential raise, corrosion current decline.Relative to binary Mg-Ge alloy, the interpolation of Ca and Zn element also effectively improves the corrosion resistance nature of material.
Embodiment 5,
Adopting the method in embodiment 4 to prepare test sample, is 1.25cm according to surface-area/vat liquor volume ratio after uv irradiating sterilizing 2h
2ml
-1standard system for vat liquor (sample after sterilizing is immersed in not containing serum MEM substratum in, after 72 hours, taking out substratum carries out centrifugal, the supernatant liquor obtained is vat liquor), adopt human osteosarcoma cell MG63 and mouse bone-forming cell MC-3T3 to evaluate Mg-Ge-(Ca, Zn that the present invention obtains) cytotoxicity of alloy.
Cell is cultivated the cell survival rate after 1d, 3d and 5d respectively as shown in Figure 4 in vat liquor, can be learnt by this figure, after rolling, the cytotoxicity of alloy is apparently higher than cast alloy.With the prolongation of cell incubation time in vat liquor, the survival rate of MG63 cell shows as and declines to some extent, but except rolling state Mg-3Ge, still keeps higher cell survival rate after 5 days, and its cytotoxicity is still in safety range; The survival rate of MC-3T3 cell extends without considerable change with incubation time, still keeps the survival rate of more than 100%, show that alloy vat liquor has the effect of growth promoting effects to MC-3T3 cell after 5 days.
Embodiment 6,
Be 99.95% by pure Mg(purity), pure Ge(purity is 99.9%) and pure Zn(purity be 99.999%), pure Ca(purity is 99.9%), be Ge:Zn=2.5:1.5 in mass ratio, magnesium is surplus, Ge:Ca=1.5:0.2, magnesium is that surplus mixes, be pressed into base, (vacuum tightness is 0.5atm) is sintered in vacuum sintering furnace, the step of concrete sintering is: after being warming up at a slow speed 300 DEG C with 2 DEG C/min, then be rapidly heated to 700 DEG C with 30 DEG C/min, then 4h is kept at this temperature, finally, the cold cooling of stove, the Mg-Ge-(Ca of vesicular structure is obtained with element powders mixed-sintering method, Zn) alloy.
Claims (6)
1. a Mg-Ge magnesium alloy, is characterized in that: described magnesium alloy is made up of Mg, Ge and Ca;
By weight percentage, in described magnesium alloy, the content of Ge is the content of 1.5%, Ca is 0.2 ~ 1.5%, and surplus is Mg.
2. the preparation method of magnesium alloy according to claim 1, comprises the steps: described Mg, Ge and Ca to be mixed to get mixture, at CO
2and SF
6under atmosphere protection, described mixture is carried out melting, after cooling, namely obtain described magnesium alloy.
3. method according to claim 2, is characterized in that: described method also comprises the step of described magnesium alloy being carried out mechanical workout; Described mechanical workout comprises rolling and/or rapid solidification step;
Described rolling comprises the steps: described magnesium alloy to carry out solution treatment, then successively through roughing, in roll and finish rolling.
4. the preparation method of magnesium alloy described in claim 1, comprises the steps: described Mg, Ge and Ca to be mixed to get mixture, is sintered by described mixture, then namely obtains described magnesium alloy through cooling;
Describedly be sintered to any one method following: element powders mixed-sintering method, prealloy powder sintering process and self-propagating high-temperature synthesis.
5. the method according to claim 3 or 4, is characterized in that: described method also comprises the step of the surface-coated degradable ceramic coating to described magnesium alloy;
The material of described degradable ceramic coating is one or more the arbitrary combination in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium;
The thickness of described degradable ceramic coating is 0.01 ~ 5mm;
Described degradable ceramic coating is applied by plasma spraying, galvanic deposit or differential arc oxidation method.
6. Mg-Ge magnesium alloy described in claim 1 is preparing the application in medical implant.
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| CN104046870A (en) * | 2014-07-09 | 2014-09-17 | 北京汽车股份有限公司 | High-elasticity-modulus magnesium alloy and preparation method thereof |
| CN106756860A (en) * | 2016-12-20 | 2017-05-31 | 薛亚红 | For Anticorrosion method for neodymium iron boron ferrite |
| US10711330B2 (en) | 2017-10-24 | 2020-07-14 | GM Global Technology Operations LLC | Corrosion-resistant magnesium-aluminum alloys including germanium |
| CN111101039A (en) * | 2018-10-26 | 2020-05-05 | 宝山钢铁股份有限公司 | High-strength corrosion-resistant magnesium alloy material and manufacturing method thereof |
| CN109972007B (en) * | 2019-03-20 | 2020-11-20 | 北京科技大学 | Anastomosis nail material capable of degrading Mg-Zn-Ca-M in organism and preparation method thereof |
| CN109966568B (en) * | 2019-04-11 | 2021-08-06 | 湘潭大学 | Zn-Ge-X ternary biomedical material and preparation method thereof |
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